CN101305024A - Branched fluoropolymers - Google Patents
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- CN101305024A CN101305024A CNA2006800418162A CN200680041816A CN101305024A CN 101305024 A CN101305024 A CN 101305024A CN A2006800418162 A CNA2006800418162 A CN A2006800418162A CN 200680041816 A CN200680041816 A CN 200680041816A CN 101305024 A CN101305024 A CN 101305024A
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
- D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
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- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
- C08F14/22—Vinylidene fluoride
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Abstract
The invention relates to the preparation of branched fluoropolymers having long chain branches and little or no gels, by a process involving polymerization at high temperatures using persulfates and optionally multifunctional initiators. The invention also relates to gel-free, branched polymers with strain hardening produced by the process.
Description
Invention field
The present invention relates to prepare and have long-chain branch and do not have or have only the seldom method of the branched fluoropolymers of gel, the aided initiating that this method relates to the use persulphate and chooses wantonly, polyreaction at high temperature.The invention still further relates to branched polymer by the gel-free with strain hardening of method for preparing.
Background of invention
Fluoropolymer is the resin of melt-processable, described resin can by such as extrude, injection moulding, spinning, many different methods extrusion blow molded and blown film form polymer architectures.Fluoropolymer is because its low surface energy and phase behavior can also be used as polymer processing aids.
Fluoropolymer resin is adding the performance in man-hour, and especially its workability, stability and reliability are controlled by the visco-elasticity of fluoropolymer resin mainly.Polymkeric substance should have strain hardening, shear-thinning behavior especially, and can well balanced melt strength and preliminary draft than (drawdown ratio).In addition, polymkeric substance must keep good solid state properties.
Usually the fluoropolymer that adopts letex polymerization to make shows moderate shear desaturation behavior, low-molecular-weight resin is shown the melt strength of difference.These fluoropolymers generally are line styles, do not show strain hardening under low rate during tensile deformation.Therefore, these fluoropolymers seldom are used for the application as blown film, extrusion blow molded, thermoforming and rigid foam.
The molecular weight that improves fluoropolymer can increase melt strength, still, makes preliminary draft than descending through regular meeting.Therefore, under without chemical process change polymer architecture condition, be difficult between the parameter of melt strength parameter and preliminary draft ratio, reach balance.Crosslinked polymkeric substance has improved melt strength, still, is subjected to being difficult for processing and often higher restriction of gel content.
A kind of method that reaches above-mentioned balance of properties is to introduce long-chain branch on main polymer chain.Can consider various structures like this and therefore various melt rheological property matter are arranged.There is multiple currently known methods that long chain branching (LCB) is introduced on the main polymer chain.
In olefinic polymerization, use catalyzer, form the polyethylene of controlled long chain branching by making ethene and high alpha-olefin copolymerization, as at WO 9612744 and Macromolecules (2003), 36 (24), described in the 9014-9019.
To polycondensation polymer, use the functional monomer to form LCB (described in WO 2001066617), or the diacid chains of formation branching (as Polymer Preprints (ACS Polymer Chemistry) (2002), 43 (2), described in the 472-473).
Verified, by the very difficult high branched polymers that obtains gel-free of letex polymerization.Journal ofPolymer Science，Part A：Polymer Chemistry(1997)，35(5)，827-858。
By using polyfunctional initiator such as Luperox JWEB, can in polystyrene, reach long chain branching (Kasehagen etc., Society of Plast ics Engineering, 2002 prceedings).
Fluorochemical monomer is very responsive to taking the hydrogen effect by force, and may not necessarily use the ordinary method of carrying out branching in other monomer systems as described above.
Adopted several method to improve long chain branching in the fluoropolymer.MacromolecularSymposia (2004), 206 (Polymer Reaction Engineering V), 347-360 disclose reversible chain transfer based on iodine and are used in and form long-chain branch in the polymkeric substance.Can during polyreaction, two kinds of interconnective bifunctional molecules of different polymer chains be caused branching by using.This is a kind of two-step approach, must prepare telomer separately in this method.The present invention does not use this telomer just can meet the requirements of the result.
Macromolecules (2000), 33 (5), 1656-1663 discloses fluoropolymer, and the long-chain branch of trifunctional produces by changing polymkeric substance (transfer-to-polymer) mechanism in this fluoropolymer.
Among the present invention, do not use the fluorizated diolefine just can reach branching.US 5612419 and US5585449 disclose a kind of two-step approach of using diolefine to prepare the fluorizated thermoplastic elastomer.
Be disclosed in the U.S. Patent application 11/157225 by the method for using a small amount of irradiation to carry out branching.
Therefore need such branched fluoropolymers, that is, the shear-thinning that branched fluoropolymers is lower begins, and melt strength and preliminary draft than between have well balancedly, can keep good solid state properties simultaneously.
Be surprised to find, the fluoropolymer with long chain branching of top listed character can obtain under the high-temperature by using some persulfate initiator very much.This branching can be optimized by using aided initiating.An attendant advantages of this method is that this branched fluoropolymers only contains small amount of gel or do not contain gel.These novel materials can be applied to require the field of good melt rheological property, as blown film, spinning, extrusion blow molded, thermoforming and rigid foam.
Summary of the invention
The present invention relates to a kind of method that forms branched fluoropolymers, this method comprises:
A) one or more fluorochemical monomers, persulfate initiator and liquid vehicle are mixed, form reaction mixture;
B) the reacting by heating mixture is to the temperature that is higher than 100 ℃; With
C) during polymerization process, postpone the constant feed of persulfate initiator in the reaction mixture,
Have the branched fluoropolymers of long-chain branch with generation, the gel content of this branched fluoropolymers is less than 5 weight %.
The invention still further relates to a kind of branched fluoropolymers, this polymkeric substance has following performance:
A) more than or equal to the side chain of the critical molecular weight between tangling;
B) strain hardening;
C) turning radius ratio is less than 1, and wherein, described turning radius ratio is to determine divided by the turning radius of the linear fluoropolymer of same chemical constitution and molecular weight by the branched fluoropolymers turning radius;
D) gel is less than 5 weight %; With
Weight-average molecular weight is 20,000-2,000,000g/mol.
The accompanying drawing summary
Fig. 1: illustrate and use the vibration-rheological instrument, at the 230 ℃ of complex viscosities that the simple linear polymer of branched polymer of the present invention and comparative example is measured and the relation curve of frequency.
Fig. 2: illustrate and use vibration strain rheometer (oscillatory strain rheometer), at the 230 ℃ of storage moduluss that the simple linear polymer of branched polymer of the present invention and comparative example is measured and the relation curve of frequency.
Fig. 3: illustrate and use the long filament stretching device, in conjunction with capillary rheometer at 180 ℃ of melt strengths that the simple linear polymer of branched polymer of the present invention and comparative example is measured with preliminary draft than changing.
Fig. 4: illustrate and use stretching rheometer, at 180 ℃ of extensional viscosity and time relation curves that the simple linear polymer of branched polymer of the present invention and comparative example is measured.
Fig. 5: illustrate with the capillary rheometer under the standard conditions, and use the casement of 30/1 ratio, the apparent viscosity that the simple linear polymer of branched polymer of the present invention and comparative example is measured changes with apparent shear rate.
Detailed Description Of The Invention
The ratio of used term " prestretched ratio " the expression polymer amount that can stretch in the melting attitude and the speed when polymer-extruded herein.
Used term " is sheared rareization " expression viscosity is descended with shearing speed herein. Known, to compare with the line style polymer, the shearing that fluidized polymer is lower is rare to melt the beginning. In some situation, the slope of the slope of its viscosity shear rate curve during greater than the line style polymer.
The present invention relates to prepare and have long-chain branch and only contain a small amount of gel or do not contain the method for the branched fluoropolymers of gel, the method comprises uses persulfate and optional multifunctional aided initiating, carries out polymerization at high temperature.
The present invention uses persulfate initiator under high polymerization temperature, with the preparation branched fluoropolymers. The example that can be used for persulfate initiator of the present invention includes but not limited to: sodium peroxydisulfate, potassium peroxydisulfate and ammonium persulfate. Potassium peroxydisulfate is as the initator of fluorochemical monomer, and common known potassium peroxydisulfate can not cause branching in the fluoropolymer that generates. When potassium peroxydisulfate was used for 80 ℃ of polymerization of vinylidene fluoride, branching did not occur. Find that in surprise potassium peroxydisulfate has obvious long chain branching when being used as the fluorochemical monomer initator for 120 ℃ in the fluoropolymer that generates.
The addition of persulfate in reactant mixture (take the total monomer weight that adds this reactant mixture as benchmark) is about 0.01-1.0 % by weight, preferred 0.01-0.4 % by weight. Because the half-life of persulfate initiator when high temperature is shorter, method of the present invention is included in and adds continuously initator in the reactor.
Although use persulfate initiator can reach branching as unique initator, it is useful using one or more aided initiatings. Use aided initiating can additionally control side chain quantity and the type that produces in the fluoropolymer. In one embodiment, aided initiating is difunctionality, although the present invention has also considered simple function initator and Multifunctional initiator. The example that can be used as in the present invention aided initiating includes but not limited to: diperoxy compound initator, and such as peroxidating two uncle's amyl groups and the positive butyl ester of 4,4-two (t-butyl peroxy) valeric acid. Take the monomer total amount as benchmark, the aided initiating consumption is 0-1%, preferred 0.01-0.3%.
Term " fluorochemical monomer " or the statement " fluorinated monomer " but the expression polymerization alkene, this alkene contains at least one fluorine atom, fluoro-alkyl or fluoroalkyl of linking to each other with two keys of alkene polymerization reaction take place. The polymer that term " fluoropolymer " expression forms by at least a fluorochemical monomer of polymerization, comprise with regard to its person's character it being the homopolymers, copolymer, three membered copolymers of thermoplasticity and multipolymer more, thermoplasticity represents that these polymer can flow after applying heat, be formed with the parts (useful piece) of usefulness, as carrying out with extruding in the processing at molding. The common mistake of thermoplastic poly compound has the crystal fusing point.
Can be used for thermoplastic poly compound of the present invention is the homopolymers that forms by polymerization of vinylidene fluoride (VDF), the copolymer of inclined to one side difluoroethylene, three membered copolymers and multipolymer more, wherein vinylidene fluoride units accounts for more than 70% of all monomeric unit gross weights of polymer, be preferably greater than 75% of unit gross weight, the copolymer of inclined to one side difluoroethylene, three membered copolymers and more multipolymer can make by making inclined to one side difluoroethylene and one or more monomer reactions that are selected from lower group: PVF, trifluoro-ethylene, tetrafluoroethene, α-alkene that one or more are partially or completely fluoridized, such as 3,3,3-three fluoro-1-propylene, 1,2,3,3,3-five fluorine propylene, 3,3,3,4,4-five fluoro-1-butylene and hexafluoropropenes, partially fluorinated alkene hexafluoro-isobutene, perfluorinated vinyl ether, such as perfluorinated methyl ethylene ether, the perfluor ethyl vinyl ether, perfluor n-pro-pyl ethene ether and perfluor-2-propoxyl group propyl vinyl ether, fluoridize Dloxole alkene, such as perfluor (1,3-Dloxole alkene) and perfluor (2,2-dimethyl-1,3-Dloxole alkene), allyl monomer, partially fluorinated allyl monomer or fluoridize allyl monomer, such as 2-hydroxyl ethyl alkene propyl ether or 3-allyloxy propane diols, ethene or propylene. Preferred copolymer or three membered copolymers are formed by PVF, trifluoro-ethylene, tetrafluoroethene (TFE) and hexafluoropropene (HFP).
Particularly preferred copolymer is the copolymer that comprises the VDF of about 71-99 % by weight VDF and corresponding about 1-29 % by weight TFE, comprise the copolymer of the VDF of about 71-99 % by weight VDF and corresponding about 1-29 % by weight HFP (as at United States Patent (USP) the 3rd, disclose in 178, No. 399); And the copolymer that comprises the VDF of about 71-99 % by weight VDF and corresponding about 1-29 % by weight trifluoro-ethylene.
Particularly preferred thermoplasticity three membered copolymers have, three membered copolymers of VDF, HFP and TFE, three membered copolymers of VDF, trifluoro-ethylene and TFE. Particularly preferred three membered copolymers contain at least 71 % by weight VDF, and other comonomer can exist by different umbers, but the total amount of these comonomers accounts at most 29 % by weight of three membered copolymers.
Except fluorochemical monomer and initator, can also add other conventional auxiliary agent and processing aids in the reactant mixture, include but not limited to: surfactant and emulsifying agent, cosurfactant, chain-transferring agent, buffer and anti-fouling agent. They can once add when polymerisation begins in the reaction, perhaps add or add continuously with increment in whole course of reaction.
With the total monomer is benchmark, and the consumption of tensio-active agent and emulsifying agent is about 0.02-1.0 weight % usually.Preferably their consumption is about 0.05-0.5 weight %.Tensio-active agent can use as the solution form of the convenient aqueous solution of handling.Can be used for tensio-active agent of the present invention comprises: fluorochemical surfactant, 3-allyloxy-2-hydroxyl-1-propanesulfonic acid salt, polyvinyl phosphonic acids, polyacrylic acid, polyvinylsulfonic acid and their salt, polyoxyethylene glycol and/or polypropylene glycol, alkyl phosphonates.
In polyreaction, add chain-transfer agent, to regulate the molecular weight of product.Add the amount of chain-transfer agent and the activity of the concrete chain-transfer agent that addition manner depends on use, and depend on the desired molecular weight of polymer product.The chain transfer dosage that adds in the polyreaction is benchmark with the monomeric gross weight that adds in the reaction mixture, preferably is about 0.05-5 weight %, more preferably from about 0.1-2 weight %.The example that is used for chain-transfer agent of the present invention comprises: can use oxygenated compound as chain-transfer agent, as alcohols, carbonic ether, ketone, ester class, ethers.Can also use ethane, propane and halocarbon and hydrogen halocarbon (as chlorocarbon, hydrogen chlorocarbon, Chlorofluorocarbons (CFCs) and Hydrochlorofluorocarbons as chain-transfer agent.
Polymerization reaction mixture can be chosen wantonly and comprise buffer reagent, with the pH of retentive control during whole polyreaction.PH preferably is controlled at about 4-8 scope, reduces to minimum with the undesirable color that will form in the product.
In reaction, add paraffin or hydrocarbon ils as stain control agent, farthest reduce or prevent that polymkeric substance from sticking on the reactor parts.Any long-chain, saturated, hydrocarbon wax or oil all have this function.Oil that adds in the reactor or wax amount should be able to farthest reduce and form the polymkeric substance that adheres on the reactor parts.Described amount should be directly proportional with the internal surface area of reactor usually, can be at about 1-40mg/cm
2The reactor internal surface area.Paraffin or hydrocarbon ils amount preferably are about 5mg/cm
2The reactor internal surface area.
Polymerization process of the present invention is to carry out in liquid carrier medium, can carry out (letex polymerization or suspension polymerization) in water-bearing media, perhaps carries out in supercritical co.Preferred polymerization process is letex polymerization.
The key of preparation long-chain branch is to make to be reflected to be higher than 100 ℃, preferably is higher than 110 ℃, more preferably carries out under 120-150 ℃ high temperature.Persulfate initiator is under high like this temperature, and its transformation period is short and must add this initiator during polyreaction continuously.Used monomer, comonomer and other auxiliary agents can join in initial the feeding intake in the reaction, perhaps can partly join in initial the feeding intake, and rest part is delayed and sent in the reactor.
The pressure that is used for polyreaction can be at 280-20, and the 000kPa range depends on capacity, the initiator system of selection and the monomer selection of conversion unit.Polymerization pressure is preferably 2,000-11,000kPa, most preferably 2,750-7000kPa.
The fluoropolymer of the inventive method preparation is the non-gel polymer of long chain branching." gel-free " is meant the gel content of fluoropolymer herein, is benchmark with the total polymer weight, less than 5 weight %, preferably less than 2 weight %, most preferably less than 1 weight %.Gel is meant the part that is insoluble to conventional fluoropolymer solvents such as acetone, N-Methyl pyrrolidone (NMP) or DMSO under the standard dissolution conditions in the polymkeric substance.
The side chain quantity of fluoropolymer and molecular weight can be controlled by attemperation, initiator feed rate and aided initiating amount." long-chain " branching represents that average side chain is greater than the critical molecular weight between tangling herein.To polyvinylidene fluoride polymer, long chain branching is about 2,500g/mol.Except long chain branching, expection also exists short-chain branched.The weight-average molecular weight of fluoropolymer is 20,000-2,000,000g/mol scope.To the application of melt processible, molecular-weight average is preferably 100,000-600, and 000 scope, and the branched fluoropolymers of lower molecular weight can be used as processing aid.
The product of letex polymerization is a latex, and this product can this form, normally use after the solid byproducts that forms in the filtering polymerization process, but perhaps this product agglomeration separation solid can wash and dry then.In order to use with the latex form, can make latex stable by the other tensio-active agent of further interpolation, this tensio-active agent can be identical or different ionogenic surfactant, or dissimilar, as nonionic surface active agent.To solid product, this latex is with mechanical system cohesion or poly-by additive salt or acid cure, then by the method known as separating by filtration.After the separation, solid product carries out purifying by washing or additive method, and dry to use as powder, can also be processed into pellet.Solid product also can with solvent, and use as the dispersion liquid of solvent or solution.
The branched fluoropolymers of the inventive method preparation is compared with linear fluoropolymer, has improved rheological.These character can be characterized by viscograph, and this viscograph shows that lower shear-thinning begins, and lower power law index " n " is to same molecular amount higher melt strength and higher preliminary draft ratio.In addition, keep as the solid state properties of modulus and tensile strength that to contain the monomeric fluoropolymer of VF2 similar with routine.
The fluoropolymer turning radius of the present invention is less than the turning radius of the linear fluoropolymer of the similar composition of same weight-average molecular weight.
In addition, fluoropolymer of the present invention shows strain hardening.The single shaft that term used herein " strain hardening " expression material is anti-to exceed certain strain value to or the ability of biaxial stretching, show that this polymkeric substance contains side chain.
Because fluoropolymer of the present invention has improved rheological, fluoropolymer of the present invention can be applied to require the field of melt rheological property, as blown film, and spinning, extrusion blow molded, thermoforming and rigid foam.
The power law index of fluoropolymer of the present invention " n " is in the 0.25-0.5 scope.
The maximum DDR that fluoropolymer of the present invention shows is at 5-80.DDR is defined as the ratio of draw speed and extruded velocity.
Embodiment
Conventional: as to use deionized water.SURFLON 111 is provided by rising sun friend (Asahi).
LUPEROX DTA is peroxidation two tert-pentyls (CAS# 10508-09-5),
LUPEROX 230 is 4,4-two (t-butyl peroxy) n-butyl pentanoate (CAS# 995-33-5)
Comparative example 1,2 and 3 is KYNAR polymkeric substance of technical grade, make by A Kema (Arkema), be the letex polymerization of employing standard, use fluorinated surfactant and cross two isobutyl carbonate propyl ester as the initiator preparation (as United States Patent (USP) 3,2475,396; 4,569,978 and 6,187,885 is described, and later at United States Patent (USP) 3,857, improved in 827,4,076,929,4,360,652,4,569,978,6,187,885, and these patent documentations are by with reference to being incorporated in this).These polymkeric substance are simple linear polymers, and its composition is similar to the branched fluoropolymers of following embodiment with molecular weight.
Use Surflon 111 (from rising sun friend) and Potassium Persulphate and as the Luperox 230 of initiator, preparation foraflon.In 2 gallons stainless steel reactor, add 4300 gram water, the aqueous solution of 75 grams, 15 weight %Surflon, 111 tensio-active agents, 5.5 gram ethyl acetate, 1.68 gram Luperox 230.This mixture is with argon purge and stirred 10 minutes.With reactor sealing, proceed to stir, heat this reactor to 135 ℃.In reactor, feed vinylidene fluoride, make pressure reach 4600kPa.Then,, be reduced to the speed of 60 Grams Per Hours after 30 minutes, add 1.6 weight % potassium persulfate solutions continuously with the speed of 2-120 Grams Per Hour.Keep temperature of reaction at 125 ℃, add vinylidene fluoride as required, to keep reaction pressure.2.5 after hour, stop to add vinylidene fluoride.Continue to stir 10 minutes, add initiator and keep temperature.Stop to add initiator then, stir after 15 minutes, stop heating.After being cooled to room temperature, the emptying residual gas is by the latex in the stainless (steel) wire emptying reactor.Weight measurement to this latex solid shows that solid polymer is 22 weight %.
Embodiment 2
Embodiment 2 is similar to Example 1, and difference is to change Luperox 230 aided initiating amounts.In 2 gallons stainless steel reactor, add 4300 gram water, the aqueous solution of 75 grams, 15 weight %Surflon, 111 tensio-active agents, 5.5 gram ethyl acetate, 1.40 gram Luperox 230.This mixture is with argon purge and stirred 10 minutes.With reactor sealing, proceed to stir, heat this reactor to 135 ℃.In reactor, feed vinylidene fluoride, make pressure reach 4600kPa.Then,, be reduced to the speed of 60 Grams Per Hours after 30 minutes, add 1.6 weight % potassium persulfate solutions continuously with the speed of 2-120 Grams Per Hour.Keep temperature of reaction at 125 ℃, add vinylidene fluoride as required, to keep reaction pressure.2.5 after hour, stop to add vinylidene fluoride.Continue to stir 10 minutes, add initiator and keep temperature.Stop to add initiator then, stir after 15 minutes, stop heating.After being cooled to room temperature, the emptying residual gas is by the latex in the stainless (steel) wire emptying reactor.Weight measurement to this latex solid shows that solid polymer is 22 weight %.
Table 1
| Character | Comparative example 1 | |
Comparative example 2 | Embodiment 2 | Comparative example 3 | |
| Mw(kg/mol) | 263 | 300 | 290 | 350 | 424 | 588 |
| Mw/Mn | 1.9 | 2.7 | 2.0 | 2.5 | 2.3 | 3.5 |
| Mz(kg/mol) | 212 | 899 | 246 | 715 | 467 | 2,230 |
| Tm(℃) | 167.0 | 163.1 | 169.4 | 162.9 | 168.8 | 162.5 |
| ΔH(J/g) | 56.1 | 50.3 | 55.8 | 53.3 | 55.8 | 49.9 |
Table 1 has been listed the molecular weight of the example of enumerating.Testing method is standard classical size exclusion chromatography (SEC), in conjunction with multi-angle scattering of light (MALS).Also having reported fusing point and melting heat, is that employing standard DSC technology is at the second-heating period detecting.
Fig. 1 illustrates by the vibration strain rheometer at the complex viscosity of 230 ℃ of mensuration and the relation curve of frequency.Embodiment 1,2 compares with comparative example with 3, shows that viscograph rotates.This rotation can be by characterizing than low viscosity under higher low frequency viscosity and the upper frequency.This phenomenon is called shear-thinning.This structure of representing this polymkeric substance changes to branching from line style.Can see that branched polymer shows that lower shear-thinning begins.
Fig. 2 illustrates the relation curve of vibration strain rheometer in the storage modulus and the frequency of 230 ℃ of mensuration.Show storage modulus when having improved low frequency among the embodiment 1,2 and 3, show because of existing chain branching to have snappiness.
Fig. 3 illustrates by the long filament stretching device, in conjunction with the melt strength of capillary rheometer determining with preliminary draft than changing.Extrude long filament by casement in 180 ℃, stretch with the constant acceleration then.For same molecular amount or viscosity, the sample of branching shows higher melt strength and low preliminary draft ratio.
Table 2
| Sample | Maximum melt strength (mN) | Maximum DDR |
| Comparative example 1 | 50 | 62 |
| |
150 | 30 |
| Comparative example 2 | 115 | 37 |
| Embodiment 2 | 165 | 10 |
| Comparative example 3 | 300 | 5 |
| |
280 | 13 |
Table 2 is listed maximum stretching force and preliminary draft ratio.
Fig. 4 illustrates by stretching rheometer, at the extensional viscosity and the time relation curve of 180 ℃ of mensuration.Measure the LVE observed value by the vibration strain rheometer,, adopt Trouton's law that this viscosity is converted to zero extensional viscosity to determine zero-shear viscosity.By stretching rheometer, with 5s
-1Rate of extension is measured the extensional viscosity observed value.Determined in this area that simple linear polymer (as Kynar comparative example 1,2 and 3) does not show that transient state zero extensional viscosity changes.Branched polymer of the present invention shows transient state zero extensional viscosity change (showing the strain hardening behavior).
Fig. 5 illustrates by capillary rheometer, in standard conditions, and uses the apparent viscosity of the casement mensuration of 30/1 ratio to change with apparent shear rate.
Table 3
| Sample | Melt viscosity (thousand pools) | Ratio of expansion |
| Comparative example 1 | 11.7 | 1.14 |
| |
12.0 | 2.39 |
| Comparative example 2 | 25.0 | 1.54 |
| Embodiment 2 | 20.4 | 1.92 |
| Comparative example 3 | 33.6 | 1.67 |
| |
32.9 | 1.87 |
Table 3 is listed in 180 ℃ and 110sec
-1Melt viscosity.Use laser beam to measure ratio of expansion with dynamical fashion.The Higher expansion ratio of the PVDF of branching shows snappiness, is the result who has side chain.
Claims (10)
1. method that forms branched fluoropolymers, this method comprises:
A) one or more fluorochemical monomers, persulfate initiator and liquid vehicle are mixed, form reaction mixture;
B) the reacting by heating mixture is to the temperature that is higher than 100 ℃; With
C) during polymerization process, postpone the constant feed of persulfate initiator in the reaction mixture,
Have the branched fluoropolymers of long-chain branch with generation, the gel content of this branched fluoropolymers is less than 5 weight %.
2. the method for claim 1 is characterized in that, described reaction mixture also comprises aided initiating.
3. method as claimed in claim 2 is characterized in that, described aided initiating is the initiator of diperoxy thing.
4. the method according to any one of the preceding claims is characterized in that, described persulfate initiator is selected from following: Potassium Persulphate, Sodium Persulfate and ammonium persulphate.
5. the method according to any one of the preceding claims is characterized in that, described liquid vehicle is water or supercritical co.
6. the method according to any one of the preceding claims is characterized in that, polymerization temperature is higher than 110 ℃.
7. the method according to any one of the preceding claims is characterized in that, polymerization temperature is 120-150 ℃ of scope.
8. the method according to any one of the preceding claims is characterized in that, described fluorochemical monomer comprises the vinylidene fluoride of at least 70 weight %.
9. the method according to any one of the preceding claims is characterized in that, described reaction mixture also comprises and is selected from one or more following additives: tensio-active agent, emulsifying agent, cosurfactant, chain-transfer agent, buffer reagent and stain control agent.
10. branched fluoropolymers, this polymkeric substance has following character:
A) more than or equal to the side chain of the critical molecular weight between tangling;
B) strain hardening;
C) turning radius ratio is less than 1, and wherein, described turning radius ratio is to determine divided by the turning radius of the linear fluoropolymer of same chemical constitution and molecular weight by the branched fluoropolymers turning radius;
D) less than the gel of 5 weight %; With
E) weight-average molecular weight is 20,000-2,000,000g/mol.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/271,057 | 2005-11-10 | ||
| US11/271,057 US8557938B2 (en) | 2005-11-10 | 2005-11-10 | Branched fluoropolymers |
| PCT/US2006/035999 WO2007061488A2 (en) | 2005-11-10 | 2006-09-15 | Branched fluoropolymers |
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| US (1) | US8557938B2 (en) |
| EP (1) | EP1945684B1 (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103958553A (en) * | 2011-10-05 | 2014-07-30 | 霍尼韦尔国际公司 | Polymerization of 2,3,3,3-tetrafluoropropene and polymers formed from 2,3,3,3-tetrafluoropropene |
| CN105754027A (en) * | 2014-12-15 | 2016-07-13 | 浙江蓝天环保高科技股份有限公司 | Vinylidene fluoride polymer, and preparation method and application thereof |
| CN106659985A (en) * | 2014-07-22 | 2017-05-10 | 阿科玛股份有限公司 | High toughness hollow fiber membranes based on vinylidene fluoride polymers |
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| WO2009067422A1 (en) | 2007-11-21 | 2009-05-28 | Arkema Inc. | Photovoltaic module using pvdf based flexible glazing film |
| JP2011527375A (en) * | 2008-07-07 | 2011-10-27 | アーケマ・インコーポレイテッド | Vinylidene fluoride / 2,3,3,3-tetrafluoropropene copolymer |
| US9493595B2 (en) * | 2008-07-07 | 2016-11-15 | Arkema Inc. | Vinylidene fluoride copolymers |
| EP2409998B1 (en) * | 2010-07-23 | 2015-11-25 | 3M Innovative Properties Company | High melting PTFE polymers suitable for melt-processing into shaped articles |
| KR102157505B1 (en) * | 2013-03-04 | 2020-09-18 | 알케마 인코포레이티드 | Long chain branched fluoropolymer membranes |
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- 2005-11-10 US US11/271,057 patent/US8557938B2/en active Active
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2006
- 2006-09-15 CN CN2006800418162A patent/CN101305024B/en active Active
- 2006-09-15 WO PCT/US2006/035999 patent/WO2007061488A2/en active Application Filing
- 2006-09-15 JP JP2008540021A patent/JP5173826B2/en active Active
- 2006-09-15 EP EP06814729A patent/EP1945684B1/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103958553A (en) * | 2011-10-05 | 2014-07-30 | 霍尼韦尔国际公司 | Polymerization of 2,3,3,3-tetrafluoropropene and polymers formed from 2,3,3,3-tetrafluoropropene |
| CN103958553B (en) * | 2011-10-05 | 2018-04-06 | 霍尼韦尔国际公司 | The polymerization of 2,3,3,3 tetrafluoropropenes and the polymer formed by 2,3,3,3 tetrafluoropropenes |
| CN106659985A (en) * | 2014-07-22 | 2017-05-10 | 阿科玛股份有限公司 | High toughness hollow fiber membranes based on vinylidene fluoride polymers |
| CN105754027A (en) * | 2014-12-15 | 2016-07-13 | 浙江蓝天环保高科技股份有限公司 | Vinylidene fluoride polymer, and preparation method and application thereof |
| CN105754027B (en) * | 2014-12-15 | 2019-03-22 | 浙江蓝天环保高科技股份有限公司 | A kind of partial fluorine ethylene polymer, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009516018A (en) | 2009-04-16 |
| JP5173826B2 (en) | 2013-04-03 |
| WO2007061488A3 (en) | 2007-07-26 |
| EP1945684A4 (en) | 2010-09-22 |
| CN101305024B (en) | 2012-08-22 |
| US20070106010A1 (en) | 2007-05-10 |
| WO2007061488A2 (en) | 2007-05-31 |
| US8557938B2 (en) | 2013-10-15 |
| EP1945684B1 (en) | 2012-06-06 |
| EP1945684A2 (en) | 2008-07-23 |
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